Oxalate-bridging NdIII-based arsenotungstate with multifunctional NIR-luminescence and magnetic properties

Abstract

Oxalate bridged Nd-based arsenotungstate, K₁₄Na₆H₄[{(As₂W₁₉O₆₇(H₂O))Nd(H₂O)₂}₂(C₂O₄)]·64H₂O (1), was obtained from the reaction of K₁₄[As₂W₁₉O₆₇(H₂O)], oxalic acid, and NdCl₃·6H₂O in mildly acidic aqueous solution. The polyanion exhibits a dimeric structure in which the fully deprotonated oxalate ligands bridge two Nd^III cations and the arsenotungstate anions act as blocking ligands. The photoluminescence (PL) spectrum of 1 shows the characteristic emission peak of Nd^III in the near-infrared (NIR) region. However, the O → W charge-transfer transitions of arsenotungstate cannot effectively sensitize the emission of Nd^III cations as confirmed by the emission spectrum, due to the mismatch of the energy gap between ³T_1u → ¹A_1g (21.57 × 10³ cm⁻¹) of arsenotungstate components and ⁴F_3/2 → ⁴I_9/2 (11.43 × 10³ cm⁻¹) of Nd^III cations. Magnetic studies of 1 demonstrate its field-induced single-molecule magnet (SMM) behavior. Direct current magnetic susceptibility studies imply the weak ferromagnetic couplings present between the two neighboring Nd^III cations. In addition, the synergy between the coordination configuration of Nd^III cations and the intramolecular magnetic interaction was discussed.